Derivatives



Fatented July '13, 1

UNlTED STATES PATENT: oFFics i I amass 'rns nsarvarms' Gaetano F. DAiello, Plttslleld, Mass, assignor to General Electric Company, a corporation of New York No Drawing.

Application March 31, 1942, some No. 436,955

. is Claims. (01. zoo-24a) This invention relates to new chemical comtives. The invention especially is concerned with the production of new and useful compoundscorresponding to the following general formula:

L li...,...i...:i.

( N N BHN L Jpn $1 L wherein n represents an integer and is at least 1 and not more than 3, a is an integer and is at least 1 and not more than 2, 2 represents a mem-' ber of the class consisting of oxygen and sulfur,

7 pounds and more particularly to triazine deriva: 1

aliphatic (e. g., methyl, ethyl, propyl, isopropyl,

butyl, secondary butyl, isobutyl, butenyl, amyl,

isoamyl, herzyl, octyl, allyl, methallyl, ethallyl,

crotyl, etc., including cycloaliphstic (e. g.. cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,

cycloheptyl, etc); aryl (e. g., phenyl, diphenyl or xenyl, naphthyl, etc); aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, ailylphenyl, 2-butenylphenyl, tertiary-butylphenyl, etc.); aryl-substituted all phatic (e; g., benzyl, phenylethyl, phenylisopropyl, cinnamyl, etc); and their homologues,

as well as those groups with one or more of their hydrogen atoms substituted by, for example, a halogen. Specific examples of halogeno-substituted hydrocarbon radicals are chioromethyl, chloroethyl, chlorophenyl; dichlorophenyl, chlorocycloheml, ethyl chlorophenyl, phenyl chloroethyl, bromoethyl, bromopropyl, fluorophenyl, iodcplienyl, bromotolyl, etc. Preferably R in Formula I is hydrogen. However, there also may be produced in accordance with the present "invention compounds such, for instance, as those represented by the general formulas:

and, more 1 m r line rumc-s-ow -mi- -nnn where 2, Z andvR. have the given above with reference to Formula I. v

The new compounds of this invention may be used, for example, as pharmaceuticals, plasticizers, fungicides, insecticides. asan intermediate in the preparation of dyes and other chemical compounds, for instance imido ether, amidine, hydrazino, methylol, new compounds are especially valuable in the preparation of synthetic resinous compositions. I Thus, they may be condensed with, for instance, aldehydes, including polymeric aldehydes, hydroxy aldehydes and aldehyde-addition products, to yield condensation products of particular utility in the plastics and coating arts. Such condensation products are more fully described and are specifically claimed in my copending application Serial No. 139,390, flied April 17,

1942, and assigned to the same asslgnee as the present invention. These new compounds or their aldehyde-addition products also may be compounded with rubber, both natural and synthetic, to modify the properties of the rubber.

Various me hods may be employed to produce the chemical compounds of this invention. I

prefer to prepare them by effecting reaction be tween 2. mercapto triazine and a mono-halogenated acylated orthionoacylated urea or thlourea in the presenceof a hydrohalid'e acceptor. Illustrative examples of mercapto triazines, more particularly mercapto s-triazines (symmetrical same meanings as' v etc. derivatives. These.

instead 01 chloroacetyl urea.

' pounds urea (01' thiourea) groupings,

Example 1 This example illustrates the preparation of diamino s-triazinyl thio acetyLurea, the formula The thioammeline and sodium hydroxide were dissolved in 750 parts hot water, yielding a solution of the sodium salt of the thioammeline. The chloroacetyl urea (monoci'iloroacetyl urea) was dissolved in 2,000 parts boiling water. Both solutions were mixed together. The reaction mixture was boiled 1'01 1 hour, following initial pree cipitation oi the reaction product comprising diamino' s-triazinyl thio acetyi' urea, and finally product was removed soluble salts and dried The purified and dried product decomposed without melting at 220-210 C. It was soluble in 10% 5 -1118 hydroxide solution, but was insoluble in dioxane, ethyl alcohol.

ether, benzene and chloroform.

Example 2 LG-di-(methylamirio) a-triazinyl-2 thio acetyl area is prepared in essentially the same manner as described under Example 1 with-the exception that, instead or thioammeline, anequivalent amount '01 2-mercapto 4,6-di-(methylamino) triazine is employed Example 3 pared in essentially the same manner as described under Example 1 with the exception that,

E Dlamino s-triazinyl mammal-mo propionyi Diamino a-triazinyl thio acetyl thiourea is pre* Monoamino s-triazinyl di-(thio acetyl thiourea) Monoamino s-triazinyl di-(thio thionoacetyl .urea) Monoamino s-triazinyl di- (thio thionoacetyl thiourea) Monoamino s-triazinyl di-(alphafthio propionyl urea) Monoa.1)nino s-trlazinyl di-(beta-thic propionyl urea v M'onoamino s-triazimrl di-(alpha-thio plim i thiourea) Monoamino s-triazinyl di-(beta-thio propionyl thioure'a) a Monoamino s-triazinyl di-(alpha-thio thionopropionyl urea) i Monoamino s-triazinyl di-(beta-thlo thionopropionyl urea) v Monoamino s-triazinyl di-(alpha-thio thionopropionyl thiourea) Monoamino a-triazinyl pionyl thiourea) di-(beta-thlo i s-Triaziny1-2,4,6 Montcalm) s-'I'riazinyl-2,4,6 tri-(thlo acetyi thioure'a) s-Triazinyl-2,4,8 tri-(thio thionoacetyl urea) was cooled to 10 C. The precipitated reaction by filtration, washed free of instead 0! chloroacetyi 'urea, an equivalent tyl thiourea is used. Example 4 Diamino s-triazinvl thio thionoacetyl urea is prepared in essentially the same manner as described under Example 1 with the exception that.

amount of amount oi chlorothionoacetyl urea is employed,

Example 5 1 Diamino a-triazinyi thio thionoacetyl thiourea is prepared in essentially the same manner as, described under Example 1 with that, amoimt or chlorothionoacetyl thiourea isused.

As will be readily understood by those skilled in the art; when it is desired to produce oomcontaining a single monoamino triazinyl grou ing and two thio acetyl (or thionoacetyl) taming a triazinyl grouping and pounds oi this invention are listed below:

di-(thio acetyl urea) Moncamino a-triazlnyl or compounds con three thio acetyl urea v (or tlnonoacetyl) urea (or thiourea) groupings. .4.6-diamino l-triazinyl-2 N-(beta-thio 9 Diamino*'I-t11allny1 emit-imam mm,

an equivalent Q the exception instead 0! chloroacetyl urea, an equivalent" new chemical coms-Triazinyl-2,4,6'tri- (thio thlonoacetyl tummy s -Triaziny12,'4,6 trM'alpha-thio propionyi urea) s-Triazinyl-2,4,8 tri-(beta-thio propionyl urea), s-'Iriazinyl-2,4,6 'tri-(alphaethio propionyl unourea) s-Triazinyl-2,4,6 trl-(beta-thio propionyl duo urea) s-Triazinyl-2,4.6 trl-(alpha-thio thionoproplonyl urea) s Triazinyl 2,4,6 m; (beta thio thiopropicnyl'.

e-Triazinyl-WLG tri-(alpha-thio thionopropiony l thiourea) s-Triaziny1-2,4, 8 tri-(b'eta -t'hio' thionopropionyl thiourea) urea) urea) v Diamino g-triazinyl mono-(aipha-thio' propicnyi Diamino av i mono-(beta-thio propionyi 1 thioureal a nio m Dianuno s-trlalinil mono-(beta-thiov-thionoprm pionylureai Diamino a-triazinyl mono-(alpha-thhthiolioe 1p 'opionylthimirw Diamino 342118311111 ionylthiourea) -Diamin)o -a-t li mono-iaipha -thio urea Dlamino 8- y i v mono-(beta Diamino s-tmmmi. mono-ialpha-thio, 111ml" thioure'a) thio propionyl-ureai' I v v 4-anilino o-methyiamino a-triaflnYl-Z thin acetyi N'-phenyl.urea' A 4,8-di- (chloroethylamino) a-triazinyl-fl thio ac tyl urea I 4,B-di-(fluoroanilino) s-triaxinyl-2 alpha-thin propionyl urea 4,6-di-(iodotoluido) s-triazinyl-2 beta-thin propiomvl thlourea blow-MW Diamino s-mmnsl v and not more than tj-di-(bromonaphthylamino) s-triazinyl-2 a1- pha-thio butyryl urea 4,6-di-(methylamino) s-triazinyl-2 beta-thio alpha-phenyl butyryl urea 4,s-d1- (anilino) s-triazinyl-2 N- (beta-thio g'amma-cyolohexyl butyryl) N'-methyl thioijmmino s-triazinyl-z N-(alpha-thio propi onyl) N,N'-diphenyl urea B-toluido s-triazinyl-2,4 di-[N -(beta-thio valeryl) N' -benzyl urea] l-methylamine s-triaainyl-ZA di-(beta-thio alpha-chlorophenyl thionopropionyl urea) s-Triazinyl-2,4,6 trim-(thio acetyl) N' cyclohexyl urea] s-Tri'azinyl-2,4,6 trl-(beta-thio 'alpha-phenyl butyr'yl thiourea) where :r is an integer and is at least 1 and not 1. more than 2'. Z "represents a member or the class t-amino s-triazinyl 2-(thio acetyl urea) i-(thlo thionoacetyl urea) A Dlamino striazinyl alpha-thio beta-fluorophenyl propionyl urea Diamino s-triazinyl beta-thio alpha-bromopropyl propionvl thiourea uns) In a manner similar to that above described I with particular reference to the preparation of symmetrical triazinyl (s-triazinyl) thio acyl and thio thionoacyl ureas and thioureas, correspondin'gv derivatives oi the asymmetrical and vicinal triasincs may be prepared.

What I claim as new and desire to Letters Patent of the United States is:

1. Chemical compounds corresponding to the (amm where. n represents an integer and is at least 1 3, a: is an integer and'ls at and not more than 2, Z represents a memher 0! the class consisting oi ongen and sulfur, and R'represents a member or the class consist- 8 9 hydrosen and monovalent hydrocarbon and'halo-hydrocarbon radicals.

secure by general formula 3. Chcmical compounds as in claim 1 wherein R represents hydrogen.

3. Chemical compounds as in claim 1 wherein ais3.

all

4. Chemical compounds as in claim 1 wherein n is 2.

i chemical compounds as in a is 1.

[Chemical compounds as in claim 1 wherein 8 represents hydrogen and Z represents oxygen. 7; Chemical compounds as in claim 1 wherein 1?. represents hydrogen and a: is 1. 3. Chemical compounds corresponding to the general formula NHR claim 1 wherein carbon radicals.

in. Symmetrical mum-2,4,6 tri-(thio'acetyl 11. Monoamino s-triasinyl di-(thlo acetyl urea).

12. Diam ino s-triazinyl thio acetyl urea; 13. '1'he method 01' preparingv chemical -compounds corresponding to the general i'ormula where n represents an integer and is at least 1 and not more than 3,": is an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and suliur, and'R represents a member of the class consisting or hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, said method comprising eil'cctlng reaction, in the prwence of a hydrohalide acceptor, between (1) a mercapto triazine corresponding to the general formula where n and R have the meanings above given, and (2) a mono-halogenated compound corresponding to the general formula where X represents halogen, and n, I, Z and R have the meanings above given.

14. A method as in claim 13 wherein the hydrohalide acceptor is an alkali-metal hydroxide.

15. The method of preparing diamino s-triazinyl thio acetyl urea which comprises efiecting reaction, in the presence oi a hydrchalide acceptor, between thioammeline and chloroacetyl urea.

GAETANO F. DALELIO.

. CERTIFICATE OF'CORRECTION. i 2 Patent No. 2,52'+,286. I 1 July- 15,, 19LL5.

GAETANO F. DI'ALELIO It is hereby certified that error sppears in theprinte d specification of theabove numbered patent requiring correction as follows; Page 1, first column, line 21, for "of" read --or--; and second column, line after "etc." insert acomme; page 2, first column, line 5 for "(sktriazinel read --s-tria zine)-- line'25, first column, for bromothylamino r,ead'--bromoethylamino--; line T'jQfQr N' -diphenyl" reed --N,N -d iphenyl--; page 5, sec- 0nd column, line 60, for "thiaziny1" reed -triazi nyl-; line before "beta" insert an opening parenthesis; page lirfirst column, line '12, for

"methylamine' read -methylamino; line lit, for "tri [N read 1':r:1--[1 I-- and that the said Letters Patent should be read with this correction therein that the same may conform'to the record of the casein the Patent Office.

Signed end sealed this 51st day of August, A. D. 19145.

, h Henry VanArsdsIe, (Seal) h Acting Commissioner of Patents. 

